Walter brttck



Patented Mar. 1, 1932,

; A N O I WALTER 331101;, or 'MANNHEIM; GERMANY, YASS'IGVNOR To GENERAL'ANILINE wom;

INQ; OF YORK, 1\T. 'Y.,-A COB POBATION, OF

V I iiazenoennmfnn mnnAQumomimENzAcRmom v in Drawing Application-filed Apri1; 2 4, 1 9 3( ),"Seria1 No. 447,084, and i1; eiema ranfii 25, 1929.

oft-he benzene '5' The presentin vention relates ztd the-pro-i duction of anthraquinone-2.1"(N) benzacridones" infwhich at least the hydrogen "atoms halogen; In my-copending=appl1cati0nfor M11111 scribed a-processfor the production ofan anthraqinone 21 benza'cridone containing about 5 atoms of chlorine 'bytr'eating' 1-phenyliminoanthraquinone containing" a methyl group-in ortho position to the imino group in an organic solvent withach'lor inatk ing agent,- separating the chlorination product more readily soluble inorganic solvents from the reaction m-i'xture' and splitting'ofi' chlorine or hydrogen chlorideiilrom the'eep arated product. The product, [containlng about 5 atoms of chlorine yiel'clg on with diethylaniline' an anthraquinOne ZI- v (N) -benzacridone containing about 4 atoms of=chlorinewhich production chlorination again yields the intitial material containing- 5 atoms of chlorinef I Ihave now found that a similar product and products having a structure smnlar to ":20 that of the aforesaid chloroanthraquinone- 2.1-(N)b-enzacridone are obtained by condensing l-halogenanthraquinone-Q-carboxylic acid or derivatives thereof with 2.3.4.51 tetrahalogen anilines having a free 6-position or by condensing; l-halogenanthraquinones with free 2-position with Q-amido-bena zoio acids in which the hydrogen atoms of the benzene nucleus are substituted by halogen, acridone ring closure. then being effected.

nucleus "are The products the torrnulaf Products of the same Structure containing 4 halogen atoms are also obtained by br0- minating Bz 3.5 dihalogen anthraquinone- 2.1(N)-benzacridones which are obtainable in the aforesaid manner by employing a 3.5-

dihalogenaniline as "condensing component.

When' hIorinating the said ii 'itialmate'rial pentahalogen dervatives are. obtained containing a chlorine atom in. the 4-position of i the anthraquinone jnucleus which chlorine atom canbe replaced by hydrogen by boiling the pentachloro derivative with diethylaniline *}The aforesaid "pentahalogeng deriva- V tiv'esare also'obtainedwhenistartingwithfa" i lA g dichloroanthraquinOne Q carboiiiylic acid and condensing it with a"2;345 tetrahalogenl aniline, or with a 3.5-'dihalogen aliiline and:

obtained correspond to halogena-ting the condensation product. The? a halogen atom in the 4-position of the anthra r surprisingly quinon'e nucleus causes -a marked changeof the shades to; blue; the

products are dyestufis. which in addition' m excellent fastness properties -l1aVe" the" brill-1 liancy of the; dyestufl's :of1 the thioindi-gn;.

class which are similar to them in shade.

The following examples will further illustrate the nature of this invention, but the invention is not restricted to these examples. The parts are by weight.

Example 1 38 parts of l-chloroanthraquinone-2-carboxylic acid benzyl ester of the formula:

18 parts of m-dichloroaniline of the formula: i c 7 copper powderv are heated in 500 parts of butyl alcohol-for 24 hours at about 180 C. in an iron pressure vessel. The reaction product is filtered off by suction after cooling, washed with alcohol and boiled up with dilute hydrochloric acid and dried.

10 parts of the l-dichloroanilidoanthraquinone-2-carboxylic acid benzyl ester thus obtained corresponding to the formula:

are suspended 50 parts of dry nitrobenzene. After the addition of 5 parts of acetic acid anhydride the whole is stirred for about i 2 hoursat from 95 to 100 C. The whole anthraquinone-2.1(N) -'benzacridone of the formula: 01

nishes a violet vat from which cotton is dyed orange shades.

E'iva-mple 2 V 20 parts of l-chloroanthraquinone-Q-carboxylic acid benzyl ester are heated for 4 hours at from 185 to 195 C. with 9 parts of 2.3.4.5-tetrachloroaniline, 6.2 parts of anhydrous sodium acetate, 0.3 part of copper oxide 7 V 7 f and 30parts of nitrobenzene. After cooling 6 parts of sodium carbonate and 1 part of the melt is poured into 200 parts of concentrated sulphuric acid, care being taken that the temperature does not rise above 50 C. After stirring for 1 hour the solution is poured into Water andthe nitrobenzene is driven off with steam. The remaining l-tetraallowed to cool andthe reaction product is filtered ofl by suction. It is washed with nitroben zene, dilute caustic soda is added, and

the product is freed from nitrobenzene and alkali-soluble impurities by steam distillation and subsequent filtration.

The Bz-2.3.4.5etetrachloroanthraquinone- 2.1(N) -benzacridone thus obtained corresponding to the formula:

(ill

is a reddish yellow substance which only dissolves in organic solvents of high boiling point with great difliculty. It crystallizes from trichlorobenzene in long orange yellow matter needles. The color of the solution in concentrated sulphuric acid is orange yellow, the vat is violet and'the dyeings on cotton an orange yellow of excellent fastnessu Example '3' I 4 parts of the Bz 3.5-dichloranthraqui none-2.1(N)-benzacridone obtained according to Example 1 are suspended in parts of nitrobenzene and 0.1 part of iodine and, after heating to 70 C., 5 parts of bromine are then slowly added to the suspensionwhile stirring. In the course of about 5 hoursthe temperature is raised to the'bo'iling point,"

the reaction-'mixture being then allowed to cool. The orange yellow crystals of -Bz 3.5- dichloro Bz 2.4 dibromanthraquinone 2.1(N) -benzacridone corresponding tofthe formula concentrated sulphuricacid giving an orange yellow solution and dyes cotton fast'orange shades from a violet vat. x

Example 1; f

2 parts of the pentachloroanthraquinone- 2.1 (N) -benza'cridone obtainable according .to my copending application Ser. No. 421,727

are boiled for about 1 hour in 20 parts of diet-hylanilineQ The coloration of the solution which initially is red turns to orange yellow and brown yellow crystals separate out. After'cooling, the reaction product is,

filtered ofi, Washed with diethylaniline', ethyl alcohol and water andinay be recrystallized from trichlorobenzene in order to obtain it quite pure. The properties of the dyestufi thus produced are the same as those of the product described in Example 2.

Ewample'5 1 I 22 parts of 1.t-dichloroanthraquinone-2- carboxylic acid benzyl ester are heated for 4 hours at from 180 to 190 C. with 10 parts of 2.3.4.5-tetrachloroaniline,'6"parts of anhydrous sodium acetate, 0.3'part of copper oxide and30 parts of nitrobenzene. After The product may be recrys tallized from trichlorobenzene, it dissolves in.

ly introduced at from to C. The

.whole is kept at (the same temperature forv about 3 hours, and pis then allowed to cool when the'reaction product is filtered off by suction. It is washed with nitrobenzene and is freed from solvent by steam distillation.-

The product corresponding to the formula:

dissolves "in 7 concentrated sulphuric acid 'giv ing an orangered coloration, it gives-a violet vat and yields on" cotton a brilliant bluish roseshade of eXcellent-"fastn'ess."

The elyes'tufi maybe crystalliz'ed f-rom trichlorobenzene; in which as in all organic solvents it ijs solubjleonly with' great' di'fliculty,

, and is *thus obtained'in prismaticfneedle's; V

' 'Eadm le vrim ' 23-1partsof "the 132-2331.5-tetrachloroanthraquinone-21' (N) -benzacridone prepared 7 according to Example 2'='are suspended=in 600 partsof dry nitrobenzene and after the additionof 21partsof i-o'dine about-'90pa-rts of sulphuryilichloride are allowed to run in while stirring :atffrom 90 to 100 C. during the course-of'l hour. a The whole is; stirred at 'the same temperature ifor about '5 'hours,* the "ex cessof sul-phuryl chloride is expelled with a stream of dry air and the reaction product is filtered off by asuction after cooling. It is washedwith nitrobenzene-and'freed from solvent byasteam distillation; I The product thus obtained may be crystallized from trichlorobenzene, It correspondswith the d'yestulf 'de scribed in the foregoing example as regards its .tinctorial and other properties.

, Example? 4.3 parts of 4-132 3.5-trichloroanthra- 'quin0ne-2.1 (N') -benzachridone,. (obtainable from 1.4-dichloroanthraquinone-2-carboxylic acid by condensation with 3.5-dichloroaniline and subsequent acridone ring closure) are stirred with 0.4 part of iodine and 120 parts of dry nitrobenzen'e, and then 9 parts of sulphuryl chloride are gradually introduced at from to C. The whole is stirred for about 3 hours at the same temperature and is then allowed-to cool. The reaction product of the formula:

is filtered oif by suction and isolated in the usual manner;

Example 8 After the addition of 0.7 part of iodine to a suspension of .13 parts of the Bz 3.5-dichloroanthraquinone 2.1 (N) benzacridone obtainable according to Example 1 in 300 parts of dry nitrobenzene, 30 parts of sulphuryl chloride are gradually introduced at from 90? to 100? G. The whole is stirred for about 4 hours at the same temperature, cooled and the reaction mass filtered oif by suction. The working up is carried out in the same manner as in the foregoing examples.- The product may be crystallized from trichlorobenzene and is the pentachloroanthraquinone-2.1(N) -benzacridone hereinbefore described according to analysis and properties.

What I claim is z- 1. As new articles of manufacture pentahalogen derivatives of anthraquinone-2.1 (N) -benzacridone in, which four halogen atoms are present in the benzene nucleus and which contain the fifth halogen atom in the 4-position of the anthraquinone nucleus, which dyestuffs dissolve in concentrated sulphuric acid giving orange red solutions and dye cotton bluish red shades from violet'vats.

2. As a new article of manufacture l- Bz 2.3.4 15 pentachloroanthraquinone 2 1 (N) -benzacridone dissolving in concentrated sulphuric acid giving an orange red solution and dyeing'cotton brilliant bluish rose shades from a violet vat.

In testimony whereof I have hereunto set my hand.

WALTER BRUOK. 

